Two novel nonaheteroacene derivatives: 24,27,30,33-tetra-tert-butyl-6,8,10,17,19,21-hexaaza-1.22,4.5,11.12,15.16-tetrabenzono-nonaacene (1) and 24,27,30,33-tetra-tert-butyl-6,10,17,21-tetraaza-8,19-benzodioxin-1.22,4.5,11.12,15.16-tetrabenzono-nonaacene (2), have been successfully synthesized through cyclocondensation reactions. The studies on UV–vis and cyclic voltammogram suggest that compound 1 has a smaller bandgap comparing to that of compound 2, indicating that oxygen atoms can destroy the conjugation in compound 2. The results are further confirmed by theoretical simulation.